Intergrated process for in-field upgrading of hydrocarbons

ABSTRACT

A process is provided for in-field upgrading of heavy hydrocarbons such as whole heavy oil, bitumen, and the like using supercritical water.

FIELD OF THE INVENTION

The present invention relates to an integrated process for in-fieldupgrading of heavy hydrocarbons such as whole heavy oil, bitumen, andthe like using supercritical water.

BACKGROUND OF THE INVENTION

Oil produced from a significant number of oil reserves around the worldis simply too heavy to flow under ambient conditions. This makes itchallenging to bring remote, heavy oil resources closer to the markets.One typical example is the Hamaca field in Venezuela. In order to rendersuch heavy oils flowable, one of the most common methods known in theart is to reduce the viscosity and density by mixing the heavy oil witha sufficient diluent. The diluent may be naphtha, or any other streamwith a significantly higher API gravity (i.e., much lower density) thanthe heavy oil. A diluted, heavy crude with an API of 12 or higher willnormally be transportable by pipeline without significant problems.

For a case such as Hamaca, diluted crude oil is sent from the productionwellhead via pipeline to an upgrading facility located 120 miles away.Two key operations occur at the upgrading facility: (1) the diluentstream is recovered and recycled back to the production wellhead in aseparate pipeline, and (2) the heavy oil is upgraded with suitabletechnology known in the art (coking, hydrocracking, hydrotreating, etc.)to produce higher-value products for market. Some typicalcharacteristics of these higher-value products include: lower sulfur andnitrogen content, lower metals content, lower total acid number (TAN),lower carbon residuum content, higher API gravity, and lower viscosity.Most of these desirable characteristics are achieved by reacting theheavy oil with hydrogen gas at high temperatures and pressures in thepresence of a catalyst. In the case of Hamaca, the upgraded crude issent further to the end-users via tankers.

These diluent addition/removal processes and hydrogen-addition or otherupgrading processes have a number of disadvantages:

1. The infrastructure required for the handling, recovery, and recycleof diluent could be expensive, especially over long distances. Diluentavailability is another potential issue.2. Hydrogen-addition processes such as hydrotreating or hydrocrackingrequire significant investments in capital and infrastructure.3. Hydrogen-addition processes also have high operating costs, sincehydrogen production costs are highly sensitive to natural gas prices.Some remote heavy oil reserves may not even have access to sufficientquantities of low-cost natural gas to support a hydrogen plant. Thesehydrogen-addition processes also generally require expensive catalystsand resource intensive catalyst handling techniques, including catalystregeneration.4. In some cases, the refineries and/or upgrading facilities that arelocated closest to the production site may have neither the capacity northe facilities to accept the heavy oil.5. Coking is often used at refineries or upgrading facilities.Significant amounts of by-product solid coke are rejected during thecoking process, leading to lower liquid hydrocarbon yield. Further, thevolume of the product from the coking process is significantly less thanthe volume of the feed crude oil.

SUMMARY OF THE INVENTION

The present invention achieves the advantage of an integrated processfor in-field upgrading of heavy hydrocarbons such as whole heavy oil,bitumen, and the like using supercritical water.

In an aspect of the invention, an integrated process for in-fieldupgrading of hydrocarbons includes:

passing a hydrocarbon feed into an in-field upgrader from ahydrocarbonaceous production source;

mixing the hydrocarbon feed with a fluid comprising water that has beenheated to a temperature higher than its critical temperature in a mixingzone to form a mixture;

passing the mixture to a reaction zone;

reacting the mixture in the reaction zone under supercritical waterconditions in the absence of externally added hydrogen for a residencetime sufficient to allow upgrading reactions to occur;

withdrawing a single-phase reaction product from the reaction zone;

recovering energy from said reaction product for use in thehydrocarbonaceous production source; and

separating the cooled reaction product into gas, effluent water,converted hydrocarbons and unconverted hydrocarbons.

Optionally, the above process for in-field upgrading of hydrocarbonsfurther includes the step of applying distillation to the convertedhydrocarbons.

Optionally, the above process for in-field upgrading of hydrocarbonsfurther includes the step of blending a distillation overheads liquidwith a distillation bottoms liquid.

Optionally, the above process for in-field upgrading of hydrocarbonsfurther includes the steps of:

passing dregs to dregs processing;

contacting the dregs with a distillation overheads liquid; and

recycling extracted hydrocarbons back with the hydrocarbon feed.

Optionally, the above process for in-field upgrading of hydrocarbonsfurther includes the steps of:

-   -   mixing dregs with a fluid comprising water that has been heated        to a temperature higher than its critical temperature in another        mixing zone to form another mixture;    -   passing the other mixture to another reaction zone;    -   reacting and extracting hydrocarbons from the other mixture in        the other reaction zone under supercritical water conditions in        the absence of externally added hydrogen for a residence time        sufficient to allow upgrading reactions to occur; and    -   recycling a hydrocarbon product from the other reaction zone to        the hydrocarbon feed.

Optionally, the above process for in-field upgrading of hydrocarbonsfurther includes the step of applying distillation to the convertedhydrocarbons.

Optionally, the above process for in-field upgrading of hydrocarbonsfurther includes the step of blending a distillation overheads liquidwith a distillation bottoms liquid.

Optionally, the above process for in-field upgrading of hydrocarbonsfurther includes the step of recycling the distillation overheads liquidback with the hydrocarbon feed.

Optionally, in the above process for in-field upgrading of hydrocarbons,the hydrocarbonaceous production source is at least one selected fromthe group consisting of heavy crude oil, tar sands, bitumen, heavypetroleum crude oils, heavy vacuum gas oils, vacuum residuum, petroleumtar, coal tar, oil shale, asphaltenes and mixtures thereof.

Optionally, in the above process for in-field upgrading of hydrocarbons,the water is at least one selected from the group consisting of drinkingwater, treated or untreated wastewater, river water, lake water,seawater, produced water and mixtures thereof.

Optionally, in the above process for in-field upgrading of hydrocarbons,the water has a temperature in a range of about 374° C. to about 420° C.and a pressure in a range of about 3205 to about 4000 psia.

Optionally, in the above process for in-field upgrading of hydrocarbons,the mixture has an oil/water mass ratio in a range of about 1:1 to about1:2.

Optionally, in the above process for in-field upgrading of hydrocarbons,the reacting has a residence time in a range of about 8 min to about 30min.

Optionally, in the above process for in-field upgrading of hydrocarbons,the energy is recovered from the reaction product in a plurality of heatexchangers and steam boilers.

Optionally, the above process for in-field upgrading of hydrocarbonsfurther includes utilizing the recovered energy in an enhanced oilrecovery or steam assisted gravity drain process.

Optionally, in the above process for in-field upgrading of hydrocarbons,the dregs processing is conducted in at least one selected from thegroup consisting of a dregs washer, a mixer-settler unit, and a solidsleaching unit.

Optionally, in the above process for in-field upgrading of hydrocarbons,the distillation is conducted in a tray or packed column.

Optionally, in the above process for in-field upgrading of hydrocarbons,the operation, pressure of the mixing is in a range of about 3250 toabout 3600 psia and the operating temperature of the mixing is in arange of about 385 to about 420° C.

Optionally, in the above process for in-field upgrading of hydrocarbons,the operating pressure of the reacting is in a range of about 3205 toabout 10000 psia and the operating temperature of the reacting is in arange of about 374 to about 1000° C.

Optionally, in the above process for in-field upgrading of hydrocarbons,the operating pressure of the separating is in a range of about 150 toabout 3500 psia and the operating temperature of the separating is in arange of about 50 to about 300° C.

Optionally, in the above process for in-field upgrading of hydrocarbons,the separating, is conducted in at least one two-phase separator orthree-phase separator.

Optionally, in the above process for in-field upgrading of hydrocarbons,the operating pressure of the distillation is in a range of about 1 toabout 50 psia and the operating temperature of the distillation is in arange of about 40 to about 90° C.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process flow diagram of an embodiment of the presentinvention.

FIG. 2 is a process flow diagram of another embodiment of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

So that the above recited features and advantages of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference to theembodiments thereof that are illustrated in the appended figures. It isto be noted, however, that the appended figures illustrate only atypical embodiment of this invention and is therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

Embodiments describing the process of the present invention arereferenced in FIGS. 1 and 2. More specifically, the followingembodiments describe the processes for implementing the presentinvention.

Reactants

Water and hydrocarbons (HC), preferably heavy hydrocarbons are the tworeactants employed in a process according to the present invention.

Any heavy hydrocarbon from a hydrocarbonaceous production source can besuitably upgraded by a process according to the present invention.Preferred are heavy hydrocarbons having an API gravity of less than 20°.Also, preferably, the heavy hydrocarbons contain heteroatoms such asnitrogen and sulfur. Among the preferred heavy hydrocarbons are heavycrude oil, heavy hydrocarbons extracted from tar sands commonly calledtar sand bitumen, such as Athabasca tar sand bitumen obtained fromCanada, heavy petroleum crude oils such as Venezuelan Orinoco heavy oilbelt crudes, Boscan heavy oil, heavy hydrocarbon fractions obtained fromcrude petroleum oils particularly heavy vacuum gas oils, vacuum residuumas well as petroleum tar, tar sands and coal tar. Other examples ofheavy hydrocarbon feedstocks which can be used are oil shale, andasphaltenes.

Water

Any source of water may be used in the fluid comprising water inpracticing the present invention. Sources of water include but are notlimited to drinking water, treated or untreated wastewater, river water,lake water, seawater, produced water or the like.

Mixing

In accordance with the invention, the heavy hydrocarbon feed and a fluidcomprising water that has been heated to a temperature higher than itscritical conditions (temperature and pressure) are contacted in a mixingzone prior to entering the reaction zone. In accordance with theinvention, mixing may be accomplished in many ways and is preferablyaccomplished by a technique that does not employ mechanical movingparts. Such means of mixing may include, but are not limited to, use ofstatic mixers, spray nozzles, sonic or ultrasonic agitation. The oil andwater should be heated and mixed so that the combined stream will reachsupercritical water conditions in the reaction zone.

It was found that by avoiding excessive heating of the feed oil, theformation of byproduct such as solid residues is reduced significantly.One key aspect of this invention is to design the heating sequence sothat the temperature and the pressure of the hydrocarbons and water willreach reaction conditions in a controlled manner. This will avoidexcessive local heating of oil, which will lead to solid formation andlower quality product. In order to achieve better performance, the oilshould only be heated up with sufficient water present and around thehydrocarbon molecules. This requirement can be met by mixing oil withwater before heating up.

In FIG. 1, water is heated to a temperature higher than criticalconditions, and then mixed with oil. The temperature of heavy oil feedshould be kept in the range of about 100 to 343° C. to avoid thermalcracking but still high enough to maintain a reasonable pressure drop.The water stream temperature should be high enough to make sure thatafter mixing with oil, the temperature of the oil-water mixture is stillhigher than the water supercritical temperature. In this embodiment, theoil is actually heated by water in a direct contact heat exchange. Anabundance of water molecules surrounding the hydrocarbon molecules willsignificantly suppress condensation reactions and therefore reduceformation of coke and solid product.

The required temperature of the supercritical water stream can beestimated based on the reaction temperature and water to oil ratio.Since the heat capacity of water changes significantly in the range nearits critical conditions for a given reaction temperature, the requiredtemperature for the supercritical water stream increases almostexponentially with decreasing water-to-oil ratio. The lower thewater-to-oil ratio, the higher the temperature of the supercriticalwater stream. The relationship, however, is very nonlinear since ahigher supercritical water stream temperature leads to a lower heatcapacity (far away from the critical point).

Reaction Conditions

After the reactants have been mixed, they are passed into a reactionzone in which they are allowed to react under temperature and pressureconditions of supercritical water, i.e. supercritical water conditions,in the absence of externally added hydrogen, for a residence timesufficient to allow upgrading reactions to occur. The reaction ispreferably allowed to occur in the absence of externally added catalystsor promoters, although the use of such catalysts and promoters ispermissible in accordance with the present invention.

“Hydrogen” as used herein in the phrase, “in the absence of externallyadded hydrogen” means hydrogen gas. This phrase is not intended Toexclude all sources of hydrogen that are available as reactants. Othermolecules such as saturated hydrocarbons may act as a hydrogen sourceduring the reaction by donating hydrogen to other unsaturatedhydrocarbons. In addition, H₂ may be formed in-situ during the reactionthrough steam reforming of hydrocarbons.

The reaction zone preferably comprises a reactor, which is equipped witha means for collecting the reaction products (syncrude, water, andgases), and a section, preferably at the bottom, where any metalcontaining compounds/organometallics or solids (the “dreg stream”) mayaccumulate.

Supercritical water conditions include a temperature from 374° C. (thecritical temperature of water) to 1000° C., preferably from 374° C. to600° C. and most preferably from 374° C. to 420° C., a pressure from3205 (the critical pressure of water) to 10000 psia, preferably from3205 to 7200 psia and most preferably from 32.05 to 4000 psia, anoil/water mass ratio from 11:0.1 to 1:10, preferably from 1:0.5 to 1:3and most preferably about 1:1 to 1:2.

The reactants are allowed to react under these conditions for asufficient time to allow upgrading reactions to occur. Preferably, theresidence time will be selected to allow the upgrading reactions tooccur selectively and to the fullest extent without having undesirableside reactions of coking or residue formation. Reactor residence timesmay be from 1 minute to 6 hours, preferably from 8 minutes to 2 hoursand most preferably from 8 to 30 minutes.

Reaction Product Cooling and Heat Integration with Field Production

After the reaction has progressed sufficiently, a single phase reactionproduct is withdrawn from the reaction zone and cooled in a series ofheat exchangers and steam boilers from a temperature of about 380 to420° C. and pressure of about 3400 to 3600 psia to the final desiredcondition for phase separation which is preferably no lower than 150° C.and about 3400 psia. The first heat exchanger is a steam boiler, wherebythe reaction product is cooled to a temperature of about 300° C. fromone zone of the heat exchanger, and 80% quality steam at 900 psia steamis produced from the other zone. This steam (recovered energy fromreaction product) is sent to the bitumen production field for steaminjection in an enhanced oil recovery (EOR) operation, a steam assistedgravity drain (SAGD) operation, or any other hydrocarbon productionoperation where steam injection is required. The subsequent coolingsteps of the 300° C. reaction product may include any combination offeed-effluent heat exchange steps to preheat inlet water streams, oilstreams, and production of lower pressure steam (50 psia, 150 psia, 300psia) for internal use within the process.

Reaction Product Separation

After cooling, the reaction product stream is separated into gas,effluent water, and upgraded hydrocarbon phases. This separation ispreferably done by cooling the stream and using one or more two-phaseseparators, three-phase separators, or other gas-oil-water separationdevice known in the art. However, any method of separation can be usedin accordance with the invention.

The composition of gaseous product obtained by treatment of the heavyhydrocarbons in accordance with the process of the present inventionwill depend on feed properties and typically comprises lighthydrocarbons, water vapor, acid gas (CO₂ and H₂S), methane and hydrogen.The effluent water may be used, reused or discarded. It may be recycledto e.g. the feed water tank, the feed water treatment system or to thereaction zone.

The upgraded hydrocarbon product, which is sometimes referred to as“syncrude” herein may be upgraded further or processed into otherhydrocarbon products using methods that are known in the hydrocarbonprocessing art.

The process of the present invention may be carried out either as acontinuous or semi-continuous process or a batch process or as acontinuous process. In the continuous process, the entire systemoperates with a feed stream of oil and a separate feed stream ofsupercritical water and reaches a steady state; whereby all the flowrates, temperatures, pressures, and composition of the inlet, outlet,and recycle streams do not vary appreciably with time.

While not being bound to any theory of operation, it is believed that anumber of upgrading reactions are occurring simultaneously at thesupercritical water conditions used in the present process. In apreferred embodiment of the invention, the major chemical/upgradingreactions are believed to be:

Thermal Cracking: C_(x)H_(y)+H₂→lighter hydrocarbonsSteam Reforming: C_(x)H_(y)+2xH₂O→xCO₂+(2x+y/2)H₂Demetalization: C_(x)H_(y)Ni_(w)+H₂→Ni—HC+lighter hydrocarbonsDesulfurization: C_(x)H_(y)S_(z)+H₂→H₂S+lighter hydrocarbons

The exact pathway may depend on the reactor operating conditions(temperature, pressure, W/O mass ratio), reactor design (mode ofcontact/mixing, sequence of heating), and hydrocarbon feedstock.

Syncrude Distillation

The syncrude product is sent to a distillation column, which serves to(1) remove light ends from the syncrude prior to storage andtransportation, and (2) to provide an overhead liquid stream that islighter (i.e., higher API) than the syncrude feed. A portion of thisoverhead liquid stream could be recycled back to the front end of theprocess to dilute the feed hydrocarbon to ease the process (final API of12-14). Alternately, this recycle stream may also be used to extract thehydrocarbon liquids from the dregs stream (see below). The remainingportion may be blended back to the bottoms stream of the column.Preferably, the column is heated by feeding in live, steam (150 psia,188° C.) at the bottom stage of the column. The overhead of the columnis cooled by any combination of air and water cooling to achieve atemperature of about 50° C. The column may be a trayed or packed columnsuch as those known in the petroleum refining art.

Dregs Processing

The dregs stream refers to the by-product produced in the supercriticalreactor that contains water, unreacted hydrocarbon liquids, coke-likematerials, sulfur-containing materials, and metal containingcompounds/organometallics. One preferred embodiment of processing thedregs stream is to contact a portion of the overhead liquid stream fromthe syncrude distillation unit with the dregs stream in a mixer-settlerunit. The overhead liquid stream acts as a solvent for extracting thehydrocarbon liquids from the non-hydrocarbon, solid-like portion of thedregs stream. The extracted liquids are recycled back to the front endof the process to mix with the feed hydrocarbon to the supercriticalwater reactor. The non-extracted stream from the mixer-settlers areconcentrated with the solids, and is sent to a reactor solids dryerheated with 300 psia steam. The solids dryer includes a porcupineheater, screw conveyor, or any other solids drying device known in theart. Residual liquids from the non-extracted stream are vaporized,recondensed, and separated to form gaseous products (sent to fuel orflare header), possibly water (sent to water treatment unit), andhydrocarbons (recycled along with the extracted hydrocarbon liquidstreams). The solids portion are transported out via a conveyor belt orother solids-transportion method known in the art to a solids cooler,and then stored for eventual disposal or metals reclamation.

The following embodiments are illustrative of the present invention, butare not intended to limit the invention in any way beyond what iscontained in the claims which follow.

EMBODIMENT

In an embodiment of the invention illustrated in FIG. 1, a heavyhydrocarbon feed stream 101 and a water feed stream 103, havingcompositions as shown in TABLES 1 & 2 (Simulated Example Data), are fedto a mixer 130. As described in more detail above, the mixer 130 mayinclude, but is not limited to, static mixers, spray nozzles, and sonicor ultrasonic agitation. The heavy hydrocarbon feed stream 101 and thewater feed stream 103 are mixed so that a combined stream 104 will reachsupercritical water conditions. The operating pressure of the mixer 130is in the range of about 3250 to about 3600 psia. The operating,temperature of the mixer 130 is in the range of about 385 to about 420°C. The oil/water mass mix ratio of the mixer 130 is in the range ofabout 1:0.5 to about 1:3.

The combined stream 104 is fed to a reactor 140. The combined stream 104has a composition as shown in TABLES 1 & 2. As described in more detailabove, the reactor 140 may include, but is not limited to, a reactorwhich is equipped with a means for collecting reaction products(syncrude, water, and gases), and a section, preferably at the bottom,where any metal containing compounds or solids (the “dreg stream”) mayaccumulate.

The reactants in the combined stream 104 are allowed to react undertemperature and pressure conditions of supercritical water, for aresidence time sufficient to allow upgrading reactions to occur.

The operating temperature of the reactor 140 is in the range of about374° C. to about 1000° C. The operating pressure of the reactor 140 isin the range of about 3205 to about 10000 psia. The oil/water mass ratiois in the range of about 1:0.1 to a about 1:10. The residence time ofthe reactor is in the range of about 1 min to 6 hrs.

A reactants product stream 105 is cooled and fed to a separator 150. Thereactants product stream 105 has a composition as shown in TABLES 1 & 2.As described in more detail above, the cooling may be conducted in aheat exchanger unit that includes, but is not limited to, a shell andtube heat exchanger and a plate heat exchanger. Water is cross heatexchanged with the reactants product stream 105. Due to this heatexchange, the water is vaporized into a superheated steam that may beintegrated and used in a Steam Assisted Gravity Drainage (SAGD) processin an oil field.

As described in more detail above, the separator 150 may include, but isnot limited to, one or more two-phase separators, three-phaseseparators, or other known gas-oil-water separation devices.

The reactants product stream 105 is separated into a gas stream 107, asyncrude stream 106, and an effluent water stream 108.

The operating pressure of the separator 150 is in the range of about 150to 3500 psia. The operating temperature of the separator 150 is in therange of about 50 to 300° C.

The syncrude stream 106 is fed to a separator 160. The syncrude stream106 has a composition as shown in TABLES 1 & 2. As described in moredetail above, the separator 160 may include, but is not limited to, apacked or trayed-type distillation column equipped with a reboiler andcondenser, a refluxed column with live steam injection at the bottom, ora vacuum distillation column. The operating pressure of the separator160 is in the range of about 1 to about 50 psia. The operatingtemperature of the overhead condenser is in the range of about 40 toabout 90° C.

A portion of the overheads diluent stream 109, 111 is combined with abottoms syncrude stream 110 at a weight percentage in the range of about0 to about 30%. A combined syncrude stream 112 is then fed to furtherdownstream processes or to storage for further transport.

The overheads diluent stream 109 is also recycled (stream 113) and fedto a dregs processor 170. A dreg stream 114 is also fed to the dregsprocessor 170. The dreg stream 114 has a composition as shown in TABLES1 and 2. As described in more detail above, the dregs processor 170 mayinclude, but is not limited to, a dregs washer, a mixer-settler, and asolids leaching unit. The recycle diluent stream 113 from the separator160 may be used to extract hydrocarbons from the dregs stream 114 in thedregs washer. The operating pressure of the dregs processor 170 is inthe range of about 15 to 500 psia. The operating temperature of thedregs processor 170 is in the range of about 25 to 200° C.

Although not shown in the figure, the recycle stream 113 may also be feddirectly back into the heavy hydrocarbon feed stream 101. This recycleddiluent lowers the density of the heavy hydrocarbon stream 101 fromabout 5 to 10 to about 11 to 16 API. The combining of the diluent alsoallows for a reduction in the amount of the water feed stream 103.

A solid dregs stream 115 and a wet dregs stream 116 is output from thedregs processor 170. The wet dregs stream 116 is recycled back to theheavy hydrocarbon feed stream 101 to form 102, at a percentage in therange of about 50 to 100%. The remaining portion of the wet dregs streammay be combined with the syncrude product 112, used for fuel, or sentoff to storage and transportation as a separate product stream.

In the tables below, two oil assays (one for the feed and one for thesyncrude) are modeled using a set of hydrocarbon pseudocomponents. Thenotation, Blend 1 refers to the feed while Blend 2 refers to theproduct. The notation Blend 2 (170 to 265° C.) means that the group ofcomponents in Blend 2 have a boiling point range of 170 to 265° C.Non-HC gases refers to H₂, H₂S, CO₂, N₂, O₂, and NH₃. HC-Gases mayinclude methane, ethane, propane, butane, pentane, cyclopentane,cyclohexane, and benzene. Oxygenates include phenol, heptanoic acid, andcatechol.

TABLE 1 summarizes only the major streams—some intermediate heatexchange steps, pumping steps, internal recycle streams, and offsitefacilities are not shown.

TABLE 1 Summary of Major Streams Only (Compositions in mass %) StreamNon HC BLND1 BLND1 BLND1 BLND 1 BLND 1 BLND 2 BLND 2 BLND 2 BLND 2 No HCGases 203 to 433 to 654 to 880 to 1101 to 170 to 275 to 383 to 494 to(FIG. 1) H2O Gases (C1-C6) Oxygenate 421 C 649 C 875 C 1096 C 1217 C 265C 375 C 485 C 634 C 101 <1.0 0 0 0 28.9 35.4 17.6 11.7 6.35 0 0 0 0 1020.01 0.006 0.226 0.214 24.3 29.8 14.8 9.8 5.3 15.2 0.1 0 0 103 99.4 0.050.01 0.55 0 0 0 0 0 0 0 0 0 104 66.4 0.04 0.08 0.44 8.1 9.9 4.9 3.3 1.85.0 0.10 0 0 105 67.1 0.52 0.45 0.61 0 0 0 0 0 8.3 8.1 9.2 4.9 106 0.170.03 0.4 0.36 0 0 0 0 0 26 28 29.3 15.7 107 3 57.1 37.8 0.23 0 0 0 0 01.8 0 0 0 108 99.3 0 0 0.7 0 0 0 0 0 0 0 0 0 109 0.07 0.037 1.4 1.3 0 00 0 0 95.2 1.9 0 0 110 0.076 0 0 0 0 0 0 0 0 3.9 36.4 38.8 20.8 111 0.070.037 1.4 1.3 0 0 0 0 0 95.2 1.9 0 0 112 0.076 0 0.13 0.13 0 0 0 0 012.2 33.3 35.2 18.9 113 0.07 0.037 1.4 1.3 0 0 0 0 0 95.2 1.9 0 0 114 00 0 0 28.9 35.4 17.6 11.7 6.4 0 0 0 0 115 N/A N/A N/A N/A N/A N/A N/AN/A N/A N/A N/A N/A N/A 116 0.06 0.03 1.2 1.1 $ 5.7 2.8 1.9 1.0 79.9 1.60 0

TABLE 2 Summary of Major Streams Only Stream No. Flowrate Pressure Temp(FIG. 1) (lb/hr) (psia) (° C.) 101 4.43e5 20 90 102 5.47e5 3550 343 103 1.1e6 3600 405 104 1.65e6 3500 393 105 1.63e6 3500 393 106 5.12e5 180156 107 1.35e4 175 40 108 2.74e5 175 40 109 1.24e5 25 50 110 3.87e5 30280 111 3.68e4 25 50 112 4.26e5 25 50 113 8.72e4 25 50 114 1.77e4 20 200115  4.9e3 20 50 116  1.0e5 20 76

OTHER EMBODIMENT

In another embodiment of the invention illustrated in FIG. 2, a heavyhydrocarbon feed stream 201 and a water feed stream 203, havingconditions as shown in TABLE 3 (Simulated Example Data), are fed to amixer 230. As described in more detail above, the mixer may include, butis not limited to, static mixers, spray nozzles, and sonic or ultrasonicagitation. The heavy hydrocarbon feed stream 201 and the water feedstream 203 are mixed so that a combined stream 204 will reachsupercritical water conditions. The operating pressure of the mixer 230is in the range of about 3250 to about 3600 psia. The operatingtemperature of the mixer 230 is in the range of about 385 to about 420°C. The oil/water mass mix ratio of the mixer 230 is in the range ofabout 1:0.5 to about 1:3.

The combined stream 204 is fed to a reactor 240. The combined stream 204has conditions as shown in TABLE 3. As described in more detail above,the reactor 240 may include, but is not limited to, a reactor which isequipped with a means for collecting reaction products (syncrude, water,and gases), and a section, preferably at the bottom, where any metalcontaining compounds or solids (the “dreg stream”) may accumulate.

The reactants in the combined stream 204 are allowed to react undertemperature and pressure conditions of supercritical water, for aresidence time sufficient to allow upgrading reactions to occur.

The operating temperature of the reactor 240 is in the range of about374° C. to about 1000° C. The operating pressure of the reactor 240 isin the range of about 3205 to about 10000 psia. The oil/water volumeratio is in the range of about 1:0.1 to a about 1:10. The residence timeof the reactor is in the range of about 1 min to 6 hrs.

A reactants product stream 205 is cooled and fed to a separator 250. Thereactants product stream 205 has flow conditions as shown in TABLE 3.The cooling may be conducted in a heat exchanger unit that includes, butis not limited to, a shell and tube heat exchanger and a plate heatexchanger. Water is cross heat exchanged with the reactants productstream 205. Due to this heat exchange, the water is vaporized into asuperheated steam that may be integrated and used in a Steam AssistedGravity Drainage (SAGD) process in an oil field.

As described in more detail above, the separator 250 may include, but isnot limited to, one or more two-phase separators, three-phaseseparators, or other known gas-oil-water separation devices.

The reactants product stream 205 is separated into a gas stream 206, asyncrude stream 208, and an effluent water stream 207.

The operating temperature of the separator 250 is in the range of about50 to 300° C. The operating pressure of the separator 250 is in therange of about 150 to 3500 psia.

The syncrude stream 208 is fed to a separator 260. The syncrude stream208 has conditions as shown in TABLE 3. The separator 260 may include,but is not limited to, a packed or trayed-type distillation columnequipped with a reboiler and condenser, a refluxed absorber equippedwith live steam injection at the bottoms, or a vacuum distillationcolumn. The operating pressure of the separator 260 is in the range ofabout 1 to about 50 psia. The operating temperature of the overheadcondenser is in the range of about 40 to about 90° C.

A portion of an overhead diluent stream 209, 211 is combined with abottoms syncrude stream 210 at a weight percentage in the range of about0 to 30%. A combined syncrude stream 212 is then fed to furtherdownstream processes or to storage and eventual transportation.

A portion of the overheads diluent stream 209 is also recycled (stream213) and combined with the heavy hydrocarbon feed 201, and output asstream 202. This diluent lowers the density of the heavy hydrocarbonstream from about 5 to 10 API to a range of about 11 to 16 API. Thecombining of the diluent also allows for a reduction in the amount ofthe water feed stream 203.

A dreg stream 214 is fed to a mixer 270. As described in more detailabove, the mixer may include, but is not limited to, static mixers,spray nozzles, and sonic or ultrasonic agitation. The dreg stream 214and a water feed stream 215 are mixed so that a combined stream 216 willreach supercritical water conditions. The operating pressure of themixer 270 is in the range of about 3250 to about 3600 psia. Theoperating temperature of the mixer 270 is in the range of about 385 toabout 420° C. The oil/water mass mix ratio of the mixer 270 is in therange of about 1:1 to about 1:10.

The combined stream 216 is fed to a reactor 280. The combined stream 216has conditions as shown in TABLE 3. As described in more detail above,the reactor 280 may include, but is not limited to, a reactor which isequipped with a means for collecting reaction products (hydrocarbonfraction, water, and gases), and a section, preferably at the bottom,where any metal containing compounds or solids (the “non-hydrocarbonfraction”) may accumulate.

The reactants in the combined stream 216 are allowed to react undertemperature and pressure conditions of supercritical water, for aresidence time sufficient to allow upgrading reactions to occur.

The operating temperature of the reactor 280 is in the range of about374° C. to about 1000° C. The operating pressure of the reactor 280 isin the range of about 3205 to about 10000 psia. The oil/water volumeratio is in the range of about 1:0.1 to a about 1:10. The residence timeof the reactor is in the range of about 1 min to 6 hrs.

A reactants product stream 218 is recycled back to stream 202. Thereactants product stream also includes converted and unconvertedhydrocarbons that are extracted in the reactor 280. The reactantsproduct stream 218 has conditions as shown in TABLE 3.

This recycling allows for a number of benefits: (1) the raw crude feed(stream 201) is diluted and made less viscous and less dense, whichmakes mixing and reaction easier, and (2) reaction product (stream 208)is also diluted with lower-density material, which facilitates eventualseparation of hydrocarbons from water in the separator 250.

Another dreg stream 217 is output from the bottom of the reactor 280.The dreg stream 217 includes hydrocarbon solids and metal-containingcompounds.

In TABLE 3, flowrates are reported in mbpd, which means thousands ofbarrels/day at standard liquid conditions. TABLE 3 summarizes only themajor streams—some intermediate heat exchange steps, pumping steps,internal recycle streams, and offsite facilities are not shown.

TABLE 3 Summary of Major Streams Only Stream No. Flowrate Pressure Temp(FIG. 2) (mbpd) (psia) (° C.) 201 30 3500 87 202 38.7 3500 83 203 793500 405 204 118 3500 393 205 126 3410 150 206 6.2 3410 150 207 114 3410150 208 41.3 3410 150 209 12.4 115 52 210 27 115 50 211 3.7 105 52 21231 105 50 213 8.7 105 50 214 1.2 3500 200 215 2.4 3500 390 216 13.4 3490388 217 13.4 3490 388 218 1.2 100 80

1. An integrated process for in-field upgrading of hydrocarbonscomprising: passing a hydrocarbon feed into an in-field upgrader from ahydrocarbonaceous production source; mixing the hydrocarbon feed with afluid comprising water that has been heated to a temperature higher thanits critical temperature in a mixing zone to form a mixture; passing themixture to a reaction zone; reacting the mixture in the reaction zoneunder supercritical water conditions in the absence of externally addedhydrogen for a residence time sufficient to allow upgrading reactions tooccur; withdrawing a single-phase reaction product from the reactionzone; recovering energy from said reaction product for use in thehydrocarbonaceous production source; and separating the cooled reactionproduct into gas, effluent water, converted hydrocarbons and unconvertedhydrocarbons.
 2. The process for in-field upgrading of hydrocarbonsaccording to claim 1, further comprising the step of applyingdistillation to the converted hydrocarbons.
 3. The process for in-fieldupgrading of hydrocarbons according to claim 2, further comprising thestep of blending a distillation overheads liquid with a distillationbottoms liquid.
 4. The process for in-field upgrading of hydrocarbonsaccording to claim 2, further comprising the steps of: passing dregs todregs processing; contacting the dregs with a distillation overheadsliquid; and recycling extracted hydrocarbons back with the hydrocarbonfeed.
 5. The process for in-field upgrading of hydrocarbons according toclaim 1, further comprising the steps of: mixing dregs with a fluidcomprising water that has been heated to a temperature higher than itscritical temperature in another mixing zone to form another mixture;passing the other mixture to another reaction zone; reacting andextracting hydrocarbons from the other mixture in the other reactionzone under supercritical water conditions in the absence of externallyadded hydrogen for a residence time sufficient to allow upgradingreactions to occur; and recycling a reactants product stream from theother reaction zone to the hydrocarbon feed.
 6. The process for in-fieldupgrading of hydrocarbons according to claim 5, further comprising thestep of applying distillation to the converted hydrocarbons.
 7. Theprocess for in-field upgrading of hydrocarbons according to claim 6,further comprising the step of blending a distillation overheads liquidwith a distillation bottoms liquid.
 8. The process for in-fieldupgrading of hydrocarbons according to claim 6, further comprising thestep of recycling the distillation overheads liquid back with thehydrocarbon feed.
 9. The process for in-field upgrading of hydrocarbonsaccording to claim 1, wherein the hydrocarbonaceous production source isat least one selected from the group consisting of heavy crude oil, tarsands, bitumen, heavy petroleum crude oils, heavy vacuum gas oils,vacuum residuum, petroleum tar, coal tar, oil shale, asphaltenes andmixtures thereof.
 10. The process for in-field upgrading of hydrocarbonsaccording to claim 1, wherein the water is at least one selected fromthe group consisting of drinking water, treated or untreated wastewater,river water, lake water, seawater, produced water and mixtures thereof.11. The process for in-field upgrading of hydrocarbons according toclaim 1, wherein the water has a temperature in a range of about 374° C.to about 420° C. and a pressure in a range of about 3205 to about 4000psia.
 12. The process for in-field upgrading of hydrocarbons accordingto claim 1, wherein the mixture has an oil/water mass ratio in a rangeof about 1:1 to about 1:2.
 13. The process for in-field upgrading ofhydrocarbons according to claim 1, wherein the reacting has a residencetime in a range of about 8 min to about 30 min.
 14. The process forin-field upgrading of hydrocarbons according to claim 1, wherein theenergy is recovered from the reaction product in a plurality of heatexchangers and steam boilers.
 15. The process for in-field upgrading ofhydrocarbons according to claim 1, further comprising utilizing therecovered energy in an enhanced oil recovery or steam assisted gravitydrain process.
 16. The process for in-field upgrading of hydrocarbonsaccording to claim 4, wherein the dregs processing is conducted in atleast one selected from the group consisting of a dregs washer, amixer-settler unit, and a solids leaching unit.
 17. The process forin-field upgrading of hydrocarbons according to claims 2 or 6, whereinthe distillation is conducted in a tray or packed column.
 18. Theprocess for in-field upgrading of hydrocarbons according to claim 1,wherein the operating pressure of the mixing is in a range of about 3250to about 3600 psia and the operating temperature of the mixing is in arange of about 385 to about 420° C.
 19. The process for in-fieldupgrading of hydrocarbons according to claim 1, wherein the operatingpressure of the reacting is in a range of about 3205 to about 10000 psiaand the operating temperature of the reacting is in a range of about 374to about 1000° C.
 20. The process for in-field upgrading of hydrocarbonsaccording to claim 1, wherein the operating pressure of the separatingis in a range of about 150 to about 3500 psia and the operatingtemperature of the separating is in a range of about 50 to about 300° C.21. The process for in-field upgrading of hydrocarbons according toclaim 1, wherein the separating is conducted in at least one two-phaseseparator or three-phase separator.
 22. The process for in-fieldupgrading of hydrocarbons according to claims 2 or 6, wherein theoperating pressure of the distillation is in a range of about 1 to about50 psia and the operating temperature of the distillation is in a rangeof about 40 to about 90° C.